Pressurizing-gas-producing charges containing an aminoguanidine tetrazole and an oxygen-liberating or gas-evolving additive

ABSTRACT

Novel gas-generating compositions comprising 40 to 100 weight percent aminoguanidine salts of azotetrazole of the formula:   OR OF DITETRAZOLE OF THE FORMULA:   Optional other components of such compositions include oxygenliberating or other gas-evolving substances which may be present in 0 to 60 weight percent of the composition. There are also disclosed pressurizing gas-actuated devices utilizing these compositions.

United States Patent 11 1 1111 3,719,604 Prior et al. 1 March 6, 1973PRESSURIZlNG-GAS-PRODUCING [57] ABSTRACT CHARGES CONTAINING AN Novelgas-generating compositions comprising 40 to AMINOGUANIDINE TETRAZOLEAND 100 weight percent aminoguanidine salts of AN OXYGEN-LIBERATING ORGAS- azotetrazole of the formula:

EVOLVING ADDITIVE 1 Inventors 2921121 95521, reiiqqr allls q mlSiegelin, Nuremberg, both of o Germany 'll, [73] Assignee: Dynamit NobelAG, Troisdorf, Ger- N many [22] Filed: Jan. 28, 1971 f f 21 Appl. No.:110,601

or of ditetrazole of the formula:

[30] Foreign Application Priority Data qw;

| Feb. 3, 1970 Germany ..P 20 04 620.2

c [52] U.S. Cl. ..252/186, 23/281, 252/187, (1

252/4, 252/350, 252/372, 260/157, 260/308, 423/235, 423/240 [51] Int.Cl. ..C06 d 5/00 [58] Field of Search ..252/l86, 187,372, 350, 4; o I hf h 23/28l2; 260/57 308;,23/235 240 ptiona 0t er components 0 sue compostions mclude oxygen-liberating or other gas-evolving substances whichmay be present in 0 to 60 weight per- [56] References Cited cent of thecomposition. There are also disclosed pres- FOREIGN PATENTS ORAPPLICATIONS surizing gas-actuated devices utilizing these compositions.854,770 11/1952 Germany 909,424 4/1954 Germany Primary Examiner- Herbefii 3 Gig/5f Assistant Examiner-Irwin Gluck AttorneyBurgess, Dinklage &Sprung S Claims, No Drawings PRESSURlZlNG-GAS-PRODUCING CHARGESCONTAINING AN AMINOGUANIDINE TETRAZOLE AND AN OXYGEN-LIBERATING RGAS-EVOLVING ADDITIVE This invention relates to gas-evolving systems. ltmore particularly refers to novel gas-evolving systems which arerelatively safe from detonation and explosion.

The energy of gases liberated in a chemical reaction is utilized inindustry to force liquids or solids out of a container, for example, infire extinguishes. Other devices make use of this force to actuate slidebars or bolts or to do other work. (See, for example, German patent854,770, introduction.) 7 7 7 As gas-generating charges, substances ormixtures are known for this purpose which are formulated entirely orlargely from combustible, gasand heat-evolving 1 substances. Suchsubstances, for example, as nitrocellulose powder or nitropolystyrene,are capable of burning without any independent feed of oxygen. Thesematerials may also consist of mixtures of oxygenliberating substances,such as potassium chlorate, and gas-evolving substances such as ammoniumnitrate or guanidine nitrate. (See, for example, German patents 854,770,851,919, and 909,424.)

Often the heat generated in these gas-evolving reactions is undesirable,and mixtures have therefore come into use which absorb the heat evolvedon oxidation by a concurrent endothermal process. Such mixtures conrain,for example, ammonium oxalate, or hydrocarbons which decompose in anendothermal reaction, such as cyclopentadiene. (German patents 882,825,and 1,150,914), respectively.)

What is desired in all cases is the evolution of as large a quantity ofgas as possible, without the explosive spontaneous decomposition of thecharge during such gas evolution, and maximum safety in handling, thatis to say, a high degree of insensitivity to ignition by friction andshock. In contrast to this desideratum, mixture containing fairly highproportions of guanidine nitrate, for example, have a tendency toexplosively decompose, which may result in destruction of the container.

It is therefore an object of this invention to provide a novelgas-generating composition.

Other and additional objects of this invention will become apparent froma consideration of this entire specification, including the claimshereof.

In accord with, and fulfilling these objects, one aspect of thisinvention resides in novel pressurizinggas-producing charges,particularly for use in pressurizing-gas-actuated devices, which arecharacterized by the fact that they comprise from 40 to 100 weightpercent aminoguanidine salts of azotetrazole and/or ditetrazole. Othercomponents of the composition may include oxygen-liberating and/or othergas-evolving substances which do not cause detonation. These may be usedsingly or in combination in proportion of 0 to 60 weight percent.

Azotetrazole has the formula and ditetrazole has the formula N N 111 1 Il The hydrogen atoms of these compounds have an acid reaction andconsequently form, with aminoguanidine, the corresponding salts. Thesesalts are prepared, for example, by mixing aqueous solutions of salts ofaminoguanidine, such as aminoguanidine sulfate, with aqueous solutionsof alkali salts of said tetrazoles. The insoluble salt compoundssuitable for use in accordance with the present invention precipitatefrom this reaction mixture and can be recovered by conventional chemicalengineering techniques.

Suitable oxygen-liberating optional additives are chlorates,perchlorates and nitrates of inorganic bases which are all preferred.Nitroguanidine, guanidine nitrate, nitrocellulose, nitropolystyrene,polynitrophenols, polynitrocresols or the like can also be incorporatedas oxygen liberators.

Soleiy gas-evolving optional additives which are suitable are, forexample, ammonium oxalate, urea, aminoguanidine, sugar, tartaric acid orthe like.

Catalysts promoting decomposition, such as compounds of vanadium,tungsten, molybdenum, chromium, cobalt or the like, particularly in thehighest degree of oxidation of the metal, may advantageously be added tothe compositions of this invention in a proportion of from 0.5 to 5weight percent, referred to the total mixture.

The compositions of this invention are prepared by simple mixing of theingredients. The resultant solid composition may be pressed, but this isnot absolutely necessary.

The following examples serve to illustrate this invention without beingin any way limiting thereon.

EXAMPLE 1 A mixture of 500 g of azotetrazole-aminoguanidine salt and 500g of barium nitrate was pressed into bodies which were then ignited in apressure pipe with nozzle. A strong gas jet was thus produced. Themixture furnished 350 cc gas/g of mixture. It was not ignited by theshock of a falling weight of 2 kg dropped from a height of 2 meters.

EXAMPLE 2 An intimate mixture of 700 g of ditetrazoleaminoguanidine saltand 300 g of potassium nitrate was pressed into bodies which wereignited in a pressure pipe with nozzle by the use of an electric primerpellet. The quantity of gas evolved was 400 cc/g. The mixture was notignited by the shock of a falling weight of 2 kg dropped from a heightof 2 meters.

EXAMPLE 3 A pressure composition was prepared from 50 g of bariumnitrate (Ba(NO 50 g of azotetrazoleaminoguanidine salt, 4 g of vanadiumpentoxide V 0 and 15 g of an aluminum-titanium alloy. After ignition ofthe composition by means of an ignition mixture disposed in a centralignition tube, a reaction of the composition set in with evolution ofheat. The heat generated was 768 cal/g.

EXAMPLE 4 A pressure composition was prepared from 40 g of bariumnitrate (Ba(NO and 60 g of azotetrazoleaminoguanidine salt. Afterignition of the composition by means of the ignition mixture disposed ina central ignition tube, a reaction of the composition set in withevolution of heat. The heat generated was 613 cal/g, Volumer, of evolvedgas: 440 em /g.

EXAMPLE 5 A pressure composition was prepared from 45 g of bariumnitrate (Ba(NO 45 g of azotetrazoleaminoguanidine salt and g ofamorphous boron. After ignition of the composition by means of theignition mixture disposed in a central ignition tube, a reaction of thecomposition set in with evolution of heat. The heat generated was 826cal/g, amount of evolved gas: 520 em /g.

EXAMPLE 6 A pressure composition was prepared from 30 g of bariumnitrate (Ba(NO 50 g of azotetrazoleaminoguanidine salt and g ofpotassium nitrate (K- NO After ignition of the composition by means ofthe ignition mixture disposed in a central ignition tube, a reaction ofthe composition set in with evolution of heat. The heat generated was687 cal/g.

What is claimed is:

1. A gas-producing composition comprising an aminoguanidine salt of atleast one member selected from the group consisting of azotetrazole ofthe formula:

V; HN\ //N f N II o N=N and ditetrazole of the formula:

T| II-N N and an oxygen-liberating additive or a gas-evolving additiveselected from the group consisting of ammonium oxalate, urea,aminoguanidine, sugar and tartaric acid present in an amount up to 60weight percent of the composition.

2. A composition as claimed in claim 1, wherein said oxygen-liberatingadditive is a member selected from 5 the group consisting of inorganicchlorates, perchlorates and nitrates; nitroguanidine; guanidine nitrate;nitrocellulose; nitropolystyrene;

polynitrophenols; and polynitrocresols.

3. A composition as claimed in claim 1, additionally containing about0.5 to 5 weight percent, referred to the entire composition, of a metalcompound catalyst wherein said metal is a member selected from the groupconsisting of vanadium, tungsten, molybdenum,

4. A composition as claimed in claim 3, wherein said metal is in itshighest valence state. 7

5. In a process for liberating gas under pressure in which a chargecomprising an oxygen-liberating or gasevolving mixture is ignited, theimprovement to reduce explosive spontaneous decomposition of the chargeand improve safety in handling which comprises adding to said charge anaminoguanidine salt of at leastone member selected from the groupconsisting of azotetrazole of the formula:

1 N=N Ha: 1i

C it C' H-N N 1:1

and ditetrazole of the formula:

and an oxygen-liberating additive or a gas-evolving additive selectedfrom the group consisting of ammonium oxalate, urea, aminoguanidine,sugar, and tartaric acid present in an amount up to 60 weight percent ofthe composition.

6. An improvement according to claim 5 wherein the oxygen-liberatingadditive is a member selected from the group consisting of inorganicchlorates, perchlorates and nitrates nitroguanidine; guanidine nitrate;nitropolystyrene; nitrocellulose; polynitrophenols; andpolynitrocresols.

7. An improvement according to claim 5 wherein the oxygen-liberating orgas-evolving substance additionally contains about 0.5 to 5 weightpercent, referred to the entire composition, of a metal compoundcatalyst wherein said metal is a member selected from the groupconsisting of vanadium, tungsten, molybdenum, chromium and cobalt.

8. An improvement according to claim 7 wherein said metal is in itshighest valence state.

1. A gas-producing composition comprising an aminoguanidine salt of atleast one member selected from the group consisting of azotetrazole ofthe formula:
 2. A composition as claimed in claim 1, wherein saidoxygen-liberating additive is a member selected from the groupconsisting of inorganic chlorates, perchlorates and nitrates;nitroguanidine; guanidine nitrate; nitrocellulose; nitropolystyrene;polynitrophenols; and polynitrocresols.
 3. A composition as claimed inclaim 1, additionally containing about 0.5 to 5 weight percent, referredto the entire composition, of a metal compound catalyst wherein saidmetal is a member selected from the group consisting of vanadium,tungsten, molybdenum, chromium and cobalt.
 4. A composition as claimedin claim 3, wherein said metal is in its highest valence state.
 5. In aprocess for liberating gas under pressure in which a charge comprisingan oxygen-liberating or gas-evolving mixture is ignited, the improvementto reduce explosive spontaneous decomposition of the charge and improvesafety in handling which comprises adding to said charge anaminoguanidine salt of at least one member selected from the groupconsisting of azotetrazole of the formula:
 6. An improvement accordingto claim 5 wherein the oxygen-liberating additive is a member selectedfrom the group consisting of inorganic chlorates, perchlorates andnitrates nitroguanidine; guanidine nitrate; nitropolystyrene;nitrocellulose; polynitrophenols; and polynitrocresols.
 7. Animprovement according to claim 5 wherein the oxygen-liberating orgas-evolving substance additionally contains about 0.5 to 5 weightpercent, referred to the entire composition, of a metal compoundcatalyst wherein said metal is a member selected from the groupconsisting of vanadium, tungsten, molybdenum, chromium and cobalt.